Adhesive composition comprising eutectic metal alloy nanoparticles

ABSTRACT

Provided herein is conductive adhesive composition comprising at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, a plurality of eutectic metal alloy nanoparticles, and at least one solvent. Also provided herein is an electronic device comprising a substrate, conductive features disposed on the substrate, a conductive electrical component disposed over the conductive features, and a conductive adhesive composition disposed between the conductive features and the conductive electrical component. Further disclosed herein are methods of making a conductive adhesive composition.

CROSS REFERENCE TO RELATED APPLICATIONS

This application claims the benefit of U.S. Provisional Application No. 62/713,893, filed Aug. 2, 2018, the disclosure of which is incorporated herein by reference in its entirety.

DETAILED DESCRIPTION Field of the Disclosure

This disclosure relates generally to conductive adhesive compositions comprising eutectic metal alloy nanoparticles, which, in embodiments, can be used in printed electronics. In embodiments, the adhesive compositions herein can be jetted via inkjet, aerosol jet or other forms of jetting. In various embodiments, the conductive adhesive composition comprises at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, a plurality of eutectic metal alloy nanoparticles, and at least one solvent. The conductive adhesive compositions disclosed herein can be digitally printed by aerosol jet or inkjet printing and demonstrate excellent adhesion strength, stability, and conductivity.

Background

Printed electronics, or the fabrication of electronic components using liquid deposition techniques, has recently become of great interest. Such techniques may provide potentially low-cost alternatives to conventional mainstream amorphous silicon technologies for electronic applications such as thin film transistors (TFTs), light-emitting diodes (LEDs), RFID tags, photovoltaics, printed memory, and the like. However, it has been a challenge to meet the conductivity, processing, morphology, and cost requirements for practical applications of printed electronics using liquids.

Traditional processes for the fabrication of electronic circuit elements require high temperature and pressure. Accordingly, conductive elements such as interconnects are typically formed on rigid surfaces, such as silicon. High temperatures and pressures limit the use of materials available for printed electronics, which may, for example, use flexible plastic substrates that melt at low temperatures, such as at about 150° C. or less.

Certain electrically conductive materials are known in the art for low melting temperatures and thus may be suitable for use on a wide range of substrates, including flexible plastic substrates. For example, inks comprising silver nanoparticles may have a high silver content, low viscosity, and melting temperature less than or equal to about 145° C. Thus inks comprising silver nanoparticles are capable of forming conductive elements by bonding (sintering) the silver particle at low temperatures. Despite these benefits, however, silver nanoparticle inks often do not adhere well to electronic components, thus limiting their use as interconnects.

Because it is desirable to have good adhesion between electronic components of certain electronic devices, it is known to use an anisotropic conductive adhesive, commonly referred to as a Z-axis adhesive, to connect a conductive substrate, such as a circuit board, to a conventional electronic component. If the adhesive is conductive across the entire substrate, it will interfere with the traces by providing additional paths of conductivity between the elements of the substrate. An anisotropic conductive adhesive provides electrical conductivity only in a direction perpendicular to the connected surfaces and not in a direction parallel to the surfaces. Thus, the anisotropic conductive adhesive does not create undesired additional paths of conductivity between the elements of the substrate. Anisotropic conductive adhesives may include conductive particles dispersed throughout an insulating adhesive matrix, such as an epoxy or a polymer. Known adhesives, however, are typically pastes, having a viscosity of greater than about 2500 cps. They are therefore unsuitable for use in liquid printing technologies, such as inkjet printing or aerosol jet printing.

There is thus a need in the art for jettable conductive adhesive compositions that enable printing and are suitable for fabricating interconnects as well as conductive features such as traces, electrodes, and the like on a variety of substrates, including flexible plastic substrates.

SUMMARY

Disclosed herein is a conductive adhesive composition comprising at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, a plurality of eutectic metal alloy nanoparticles, and at least one solvent. In certain embodiments of the conductive adhesive composition, the plurality of eutectic metal alloy nanoparticles comprises Field's metal, and in certain embodiments, the plurality of eutectic metal alloy nanoparticles further comprise at least one organoamine stabilizer selected from the group consisting of butylamine, octylamine, 3-methoxypropylamine, pentaethylenehexamine, 2,2-(ethylenedioxy)diethylamine, tetraethylenepentamine, triethylenetetramine, and diethylenetriamine.

In certain embodiments, the conductive adhesive composition has a solids content ranging from about 20% to about 80%, such as from about 30% to about 50%, based on a total weight of the conductive adhesive composition, and in certain embodiments, the at least one solvent is selected from the group consisting of propylene glycol methyl ether acetate, di(propylene glycol) methyl ether acetate, (propylene glycol)methyl ether, di(propylene glycol)methyl ether, methyl isobutyl ketone, diisobutyl ketone, 1-phenoxy-2-propanol. According to various embodiments, the at least one melamine resin is selected from the group consisting of a methylated poly(melamine-co-formaldehyde), butylated poly(melamine-co-formaldehyde), isobutylated poly(melamine-co-formaldehyde), acrylated poly(melamine-co-formaldehyde), and methylated/butylated poly(melamine-co-formaldehyde), and in certain embodiments, the composition has a viscosity ranging from about 2 cps to less than about 300 cps, such as less than about 100 cps, at a temperature of about 20° C. to about 30° C. In certain embodiments of the disclosure, the at least one epoxy resin is selected from the group consisting of bisphenol A diglycidyl ether, bisphenol A propoxylate diglycidyl ether, glycidyl epoxy resins, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, poly(propylene glycol) diglycidyl ether, tris-(hydroxyl phenyl)-methane-based epoxy resins, and cycloaliphatic epoxides. According to certain embodiments, the conductive adhesive composition further comprises at least one adhesion promoter, and in certain embodiments, the at least one polymer is a polyvinyl polymer selected from the group consisting of poly(4-vinylphenol), poly-p-vinylphenol, poly(vinylphenol)/poly(methyl acrylate), poly(vinylphenol)/poly(methyl methacrylate), and poly(4-vinylphenol)/poly(vinyl methyl ketone). In various embodiments of the disclosure, the conductive adhesive composition is jettable by inkjet or aerosol jet printing.

Also provided herein are methods of making a conductive adhesive composition comprising mixing at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, and at least one solvent to create a mixture; and adding a plurality of eutectic metal alloy nanoparticles to the mixture to create a conductive adhesive composition.

Also disclosed herein are electronic devices comprising a substrate, conductive features disposed on the substrate, a conductive electrical component disposed over the conductive features, and a conductive adhesive composition disposed between the conductive features and the conductive electrical component, wherein the conductive adhesive composition comprises at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, and a plurality of eutectic metal alloy nanoparticles. In certain embodiments of the methods disclosed herein, the plurality of eutectic metal alloy nanoparticles comprise Field's metal alloy, and in certain embodiments, the conductive adhesive composition has a solids content ranging from about 20% to about 80%, based on a total weight of the conductive adhesive composition.

In certain embodiments of the electronic device, the substrate is selected from the group consisting of silicon, glass, plastics, sheets, fabrics, synethic papers, and mixtures thereof, and in certain embodiments, the substrate is selected from the group consisting of polyester, polycarbonate, polyimide sheets, polyethylene terephthalate sheets, polyethylene naphthalate sheets, and mixtures thereof. In certain embodiments, the conductive features comprise an electrically conductive element formed from a metal nanoparticle conductive ink composition, and in certain embodiments, the metal nanoparticle conductive ink composition is a silver nanoparticle conductive ink composition. In various embodiments of the disclosure the conductive adhesive composition has a viscosity ranging from about 2 cps to about 300 cps at a temperature of about 20° C. to about 30° C.

BRIEF DESCRIPTION OF THE DRAWINGS

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments of the present teachings and together with the description, serve to explain the principles of the present teachings.

FIG. 1A is a schematic of an exemplary electrical device comprising a conductive adhesive composition as disclosed herein applied to the surface of a conductive ink on a substrate.

FIG. 1B is a schematic of the application of a resistor to an exemplary electrical device comprising a conductive adhesive composition as disclosed herein applied to the surface of a conductive ink on a substrate.

FIG. 1C is a schematic of the application of a resistor to an exemplary electrical device comprising a conductive adhesive composition as disclosed herein applied to the surface of a conductive ink on a substrate after force has been applied to the resistor.

FIG. 2A is a schematic of the application of a resistor to an exemplary electrical device using an anisotropic conductive adhesive composition as disclosed herein before the application of force to the resistor and/or curing of the anisotropic conductive adhesive composition.

FIG. 2B is a schematic of the application of a resistor to an exemplary electrical device using an anisotropic conductive adhesive composition as disclosed herein before the application of force to the resistor and/or curing of the anisotropic conductive adhesive composition.

It should be noted that some details of the figures may have been simplified and are shown to facilitate understanding of the embodiments rather than to maintain strict structural accuracy, detail, and scale.

DESCRIPTION OF THE EMBODIMENTS

Reference will now be made in detail to embodiments of the present disclosure. The following description is merely exemplary.

Disclosed herein are conductive adhesive compositions having many uses, for example, for printed electronics. In certain embodiments, the conductive adhesive compositions disclosed herein comprise at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, eutectic metal alloy nanoparticles, and at least one solvent.

Conventional electronics use robust interconnects such as solder balls, wire-bonding, and anisotropic conductive pastes to attach microchips, capacitors, diodes, and other circuit elements. Conductive adhesives may be used to attach conventional electronic silicon microchips to printed circuitry. It is desirable for a conductive adhesive composition to have high conductivity, such as a conductivity of at least about 1000 S/cm, high adhesive strength, low curing temperature, such as less than about 130° C., and a short curing time, such as less than about 2 hours. Most conductive adhesives currently available are pastes (e.g., having a viscosity greater than about 2500 cps), which precludes jetting by aerosol jet or inkjet printing. Disclosed herein are jettable conductive adhesive compositions having low viscosities (such as less than about 2500 cps) and low curing temperatures for the printed electronics industry.

The conductive adhesive compositions disclosed herein may have any desired viscosity. In certain embodiments, the viscosity ranges from about 2 cps to about 300 cps, such as from about 3 cps to about 200 cps, such as from about 3 cps to about 100 cps, from about 4 cps to about 50 cps, from about 5 cps to about 20 cps, or from about 6 cps to about 10 cps, as measured at about 20° C. to about 30° C. Viscosity can be measured by any suitable or desired method as known in the art, such as with an Ares G2 Rheometer from TA Instruments. Viscosity data can be obtained, for example, at 25° C. on an Ares G2 Rheometer from TA Instruments using a 50 millimeter, 0.053 micron gap. The conductive adhesive composition disclosed herein may have any feasible cure rate. In certain embodiments, the conductive adhesive composition may cure in less than about 24 hours, such as between about 30 minutes to about 12 hours or between about 1 hour to 3 hours, such as in less than about 2 hours.

In certain embodiments, the conductive adhesive compositions disclosed herein are anisotropic. As used herein, an anisotropic composition refers to a composition that is an electrical conductor in the z-axis and has low or no conductivity in the x-axis and the y-axis. As a result, anisotropic compositions are also sometimes referred to as z-axis conducting compositions. The anisotropic compositions disclosed herein provide a matrix for electrically conducting elements that are dispersed in the composition that span the z-axis and provide the electrical conduction through the composition. In certain embodiments, the conductive adhesive compositions disclosed herein do not contain any additional conductive elements other than the plurality of eutectic metal alloy nanoparticles. For example, in certain embodiments, the conductive adhesive compositions disclosed herein are free of silver particles, such as silver nanoparticles and silver flakes.

More particularly, the present disclosure provides a composition, which may be used in embodiments to form an adhesive between conventional electronic components such as resistors and printed conducted layers, constructed from various conductive compositions, such as metal ink compositions, e.g., silver nanoparticle inks. The conductive adhesive compositions disclosed herein can improve the adhesion between the substrates and conventional electronic components. Furthermore, the conductive adhesive compositions disclosed herein exhibit surprisingly improved dispersion, stability, conductivity, and adhesion. Accordingly, the resulting electrical devices formed from the present compositions have surprisingly excellent conductive properties.

Epoxy Resins

The conductive adhesive compositions disclosed herein comprise at least one epoxy resin. In certain embodiments of the conductive adhesive compositions disclosed herein, the at least one epoxy resin is a thermally-cured epoxy resin. In embodiments disclosed herein, there are eutectic metal alloy nanoparticles, such as Field's metal nanoparticles, evenly dispersed into a thermally-curable epoxy resin. The epoxy resin may, for example, be cured at about 120° C. for about 2 hours, which traps the conductive pathways into place.

The epoxy resin component may be any type of epoxy resin, including any material containing one or more reactive oxirane groups (also termed epoxy groups) as shown below.

Epoxy resins useful in embodiments disclosed herein may include aromatic, aliphatic or heterocyclic epoxy resins. The epoxies may be pure compounds or mixtures of compounds containing one, two or more epoxy groups per molecule. In some embodiments, epoxy resins may also include reactive —OH groups.

In some embodiments, the conductive adhesive compositions include glycidyl epoxy resins, such as glycidyl-ether epoxy resins, glycidyl-amine epoxy resins, and glycidyl-ester epoxy resins. Glycidyl epoxy resins are commercially available or may be prepared via a condensation reaction of an appropriate dihydroxy compound and epichlorohydrin as is known in the art.

In some embodiments, the at least one epoxy resin may include non-glycidyl epoxy resins, such as cycloaliphatic epoxy resins. Non-glycidyl epoxies are commercially available or may be formed by peroxidation of an olefinic double bond as known in the art.

Suitable epoxy resins may include those having aromatic moieties. Representative glycidyl-ether epoxy resins having aromatic moieties include diglycidyl ethers of bisphenol-A (DGEBA), which may be synthesized by reacting bisphenol-A with epichlorohydrin in the presence of a basic catalyst and which has the following structure.

In certain embodiments, x, the number of repeating units, ranges from 0 to 25, such as from about 2 to about 20 or about 5 to about 15.

DGEBA resins are commercially available and are marketed under the trade designations Epon® 828, Epon® 1001, Epon® 1004, Epon® 2004, Epon® 1510, and Epon® 1310 from Hexion, Inc., Columbus, Ohio and D.E.R.® 331, D.E.R.® 332, D.E.R.® 334, and D.E.R.® 439, available from Dow Chemical Co., Midland, Mich.

Other suitable bisphenol-A epoxy resins include Bisphenol A propoxylate diglycidyl ether, which is also commercially available, e.g., from Sigma-Aldrich, Inc. and which has the following structure:

wherein n=1.

Other suitable glycidyl ether epoxy resins comprising aromatic moieties include bis(4-hydroxyphenyl)methane (known as bisphenol F) and diglycidyl ether of bromobisphenol A (2,2-bis(4-(2,3-epoxypropoxy)3-bromo-phenyl)propane). Bisphenol-F based epoxy resins are commercially available, for example D.E.R.® 354 and D.E.R.® 354LV, each available from The Dow Chemical Company, Midland, Mich.

Additional glycidyl ether epoxy resins comprising aromatic moieties that may be used with the instant compositions include phenol and cresol novolacs. As is known in the art, these epoxies may be prepared by reacting phenols or cresols, in excess, with formaldehyde in the presence of an acidic catalyst to produce phenolic novolac resin. Novolac epoxy resins are then synthesized by reacting the phenolic novolac resin with epichlorohydrin in the presence of sodium hydroxide as a catalyst. A representative phenol novalac is depicted below, wherein “n” is a number of repeat units, which may, for example range from 0 to 5.

wherein n=0-5

Examples of epoxy phenolic novolac resins including epoxy bisphenol A novolac resins useful in some embodiments disclosed herein include those available under the tradenames D.E.R.® 431 and D.E.R.® 438 from The Dow Chemical Company, Midland, Mich., and EPON® SU-8, available from Hexion Specialty Chemicals, Columbus, Ohio.

Other suitable epoxy resins containing aromatic groups include those that can be prepared by the reaction of aromatic alcohols such as biphenyl diols and triphenyl diols and triols with epichlorohydrin. One representative compound is tris-(hydroxyl phenyl)methane-based epoxy available from Huntsman Corporation, Basel, Switzerland as Tactix® 742.

Additional suitable epoxy resins include glycidal amines. Glycidal amines are formed by reacting epichlorohydrin with an amine, such as an aromatic amine. An example of a suitable glycidal amine is tetraglycidyl methylene dianiline, which is represented by the following structure:

Additional suitable epoxy resins include aliphatic epoxy resins. Aliphatic epoxy resins are known in the art and include glycidyl epoxy resins and cycloaliphatic epoxides. Glycidyl aliphatic epoxy resins may be formed by the reaction of epichlorohydrin with aliphatic alcohols or polyols to give glycidyl ethers or aliphatic carboxylic acids to give glycidyl esters. This reaction may be done in the presence of an alkali, such as sodium hydroxide, to facilitate the dehydrochlorination of the intermediate chlorohydrin. These resins generally display low viscosity at room temperature, such as a viscosity ranging from about 10 to about 200 mPa·s. Exemplary glycidyl aliphatic epoxy resins for use in the conductive adhesive composition disclosed herein include trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, and poly(propylene glycol) diglycidyl ether, which are commercially available, for example, from Sigma-Aldrich, Inc.

Cycloaliphatic epoxides may also be included in the present compositions. Cycloaliphatic epoxides contain one or more cycloaliphatic rings in the molecule to which an epoxide ring is fused. They are formed by the reaction of cyclo-olefins with a peracid, such as peracetic acid. Cycloaliphatic epoxides suitable for use in preparing the instant compositions include 3,4-epoxycyclohexylmethyl-3,4-epoxycyclohexane carboxylate, bis(3,4-epoxycyclohexylmethyl)adipate, vinyl cyclohexane dioxide, and the like and are commercially available from, for example, Union Carbide Corporation, a subsidiary of the Dow Chemical Company, Houston, Tex.

One or more epoxy resins can be provided in the conductive adhesive compositions disclosed herein in any suitable or desired amount. In certain embodiments, the at least one epoxy resin is present in the composition in an amount ranging from about 0.01 to about 40 percent, such as from about 5 to about 35 percent, or from about 10 to about 25 percent, by weight, based on the total weight of the composition.

Polyvinyl Phenol

The conductive adhesive compositions disclosed herein may comprise at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals. Polyvinyl phenols can include, for example, the following: poly(4-vinylphenol), poly-p-vinylphenol, poly(vinylphenol)/poly(methyl acrylate), poly(vinylphenol)poly(methyl methacrylate), and poly(4-vinylphenol)poly(vinyl methyl ketone).

The polyvinyl phenol can be provided in the composition in any suitable or desired amount. The amount of the polyvinyl phenol present in the instant conductive adhesive composition in accordance with the present disclosure may range from about 1 wt % to about 20 wt %, such as from about 1 wt % to about 10 wt %, and from about 1 wt % to about 5 wt %, based on the total weight of the conductive adhesive composition.

Polyvinyl Butyral

The conductive adhesive compositions disclosed herein may comprise at least one of polyvinyl phenols and polyvinyl butyrals. As used herein, “polyvinyl butyral” refers to a product obtained from the hydrolysis of polyvinyl acetate to form polyvinyl alcohol or a polyvinyl alcohol polymer containing residual vinyl acetate groups; the resulting polyvinyl alcohol product being reacted with butyraldehyde under acidic conditions to form a polyvinyl butyral containing various amounts of acetate, alcohol and butyraldehyde ketal groups. In some embodiments, the polyvinyl butyral is in the form of a powder or a pellet. Methods of preparing polyvinyl butyral are known in the art and are described for example in U.S. Patent Publication No. 2012/0043512, which is herein incorporated by reference in its entirety.

Polyvinyl butyral for use in the present composition may be represented by the following formula:

wherein A, B and C represent a proportion of the corresponding repeat units expressed as a weight percent, wherein each repeat unit is randomly distributed along a polymer chain, and wherein the sum of A, B and C is about 100 weight percent.

In some embodiments, A is independently about 70 weight percent to about 95 weight percent, about 75 weight percent to about 90 weight percent, or about 80 weight percent to about 88 weight percent; B is independently about 5 weight percent to about 25 weight percent, about 7 weight percent to about 20 weight percent or about 11 weight percent to about 18 weight percent, such as about 17.5 weight percent; C is independently about 0 weight percent to about 10 weight percent, about 0 weight percent to about 5 weight percent or about 0 weight percent to about 3 weight percent, such as about 2.5 weight percent.

In some embodiments, the polyvinyl butyral of Formula VI has an average molecular weight (M_(n)) of about 10,000 to about 300,000 Daltons (Da), about 40,000 to about 200,000 Da or about 25,000 to about 150,000 Da. A representative composition of the polyvinyl butyral constitutes, on a weight basis, about 11% to 25% hydroxyl groups, calculated as polyvinyl alcohol, about 0% to about 2.5% acetate groups calculated as polyvinylacetate, with the balance being vinyl butyral groups, for example, about 80 wt % to about 88 wt %.

Suitable polyvinyl butyral for use with the conductive adhesive compositions disclosed herein are commercially available and include, for example, Butvar® B-79 (available from Monsanto Chemical Co., St. Louis, Mo.) having a polyvinyl butyral content of about 88 wt %, a polyvinyl alcohol content of about 11.0 wt % to about 13.5 wt %, and a polyvinyl acetate content of less than about 2.5 wt %, wherein the average molecular weight of Butvar® B-79 is from about 50,000 to about 80,000 Da. In certain embodiments, Butvar® B-76 (Monsanto Chemical Co.) may be used in the conductive adhesive composition. Butvar® B-76 has a polyvinyl butyral content of about 88% by weight, a polyvinyl alcohol content of about 11.5 wt % to about 13.5 wt %, and a polyvinyl acetate content of less than about 2.5 wt %, with an average molecular weight of about 90,000 to about 120,000 Da. Suitable polyvinyl butyrals for use with the conductive adhesive compositions may also include, for example, Butvar® B-72, Butvar® B-74, Butvar® B-90, and Butvar® B-98 (available from Monsanto Chemical Co., St. Louis, Mo.).

The polyvinyl butyral can be provided in the composition in any suitable or desired amount. The amount of the polyvinyl butyral present in the instant conductive adhesive composition in accordance with the present disclosure may range from about 1 wt % to about 20 wt %, such as from about 1 wt % to about 10 wt %, and from about 1 wt % to about 5 wt %, based on the total weight of the conductive adhesive composition.

Melamine Resin

In some embodiments, the conductive adhesive composition further includes a cross-linking agent, such as a melamine resin, such as a melamine-formaldehyde based polymer. As used herein, the term “melamine-formaldehyde based polymer” refers to polymers formed by a condensation reaction of melamine (1,3,5-triazine-2,4,6-triamine) with formaldehyde (CH₂O). In some embodiments, the free hydroxyl groups of the polyvinyl phenol and/or polyvinyl butyral may bond with the melamine-formaldehyde based polymer. Thus, the polyvinyl phenol and/or polyvinyl butyral may be substituted with or “cross-linked” by the melamine-formaldehyde based polymer.

Any suitable or desired melamine-formaldehyde based polymer may be included in the conductive adhesive compositions disclosed herein. In some embodiments, the poly(melamine-co-formaldehyde) based polymer is represented by the following chemical structure:

where R is independently selected from hydrogen (H) and an alkyl, such as methyl, ethyl, propyl, isopropyl, butyl, pentyl, hexyl, and isomers thereof, and in is a number of repeats of the poly(melamine-co-formaldehyde). For example, m may be a number between about 1 and about 10. As a non-limiting example, the number molecular weight (Mn) range for the poly(melamine-co-formaldehyde) based polymer may be from about 300 grams/mole to about 1,500 grams/mole. Suitable poly(melamine-co-formaldehyde) based polymers may be obtained commercially from Sigma-Aldrich, Inc. (Saint Louis, Mo.), a subsidiary of Merck KGaA.

In another embodiment, the melamine-formaldehyde based polymer is an acrylated melamine-formaldehyde based polymer, represented by the following Formula X, wherein “m” is the number of repeats of the poly(melamine-co-formaldehyde), such as between 1 and 10, and R is H, CH₃ or C₄H₉.

In certain embodiments, m ranges from about 1 to about 10, such as about 2 to about 8 or about 3 to about 7.

Acrylated melamine-formaldehyde based polymers are commercially available from Sigma-Aldrich, Inc., for example, and may have a molecular weight ranging from about 390 grams/mole to about 1,500 grams/mole.

In some embodiments, the poly(melamine-co-formaldehyde) based polymer is selected from the group consisting of methylated poly(melamine-co-formaldehyde), butylated poly(melamine-co-formaldehyde), isobutylated poly(melamine-co-formaldehyde), acrylated poly(melamine-co-formaldehyde), methylated/butylated poly(melamine-co-formaldehyde), and combinations thereof.

The poly(melamine-co-formaldehyde) based polymer can be provided in the conductive adhesive composition in any suitable or desired amount. In some embodiments, the poly(melamine-co-formaldehyde) polymer is present in an amount ranging from about 0.5 percent to about 15 percent, such as from about 1 percent to about 10 percent, or from about 1 percent to about 5 percent, by weight, based on the total weight of the conductive adhesive composition.

Eutectic Metal Alloy Nanoparticles

The conductive adhesive compositions disclosed herein comprise a plurality of eutectic metal alloy nanoparticles. Suitable eutectic metal alloys for use in the present composition include those eutectic metal alloys having a melting point lower than that of the melting point of the substrate upon which a conductive ink composition may be deposited and sintered. For example, in certain embodiments, the melting points of suitable eutectic metal alloys may be about 140° C. or less, such as about 55° C. to about 75° C., about 60° C. to about 65° C., or about 60.5° C. Eutectic metal alloys may be comprised of, for example, at least two metals chosen from bismuth, lead, tin, cadium, zinc, indium, gallium, and thallium. For example, the eutectic metal alloys may include at least two of bismuth, tin, indium, and gallium, or, in certain embodiments, the eutectic metal alloy disclosed herein may include indium, bismuth, and tin. In certain embodiments, the eutectic metal alloy is chosen from In_(51.0)Bi_(32.5)Sn_(16.5), i.e., Field's Metal (which may, for example, have a melting point of about 60.5° C.), Bi₅₈Sn₄₂ (which may, for example, have a melting point of about 138° C.), In_(66.3)Bi_(33.7) (which may, for example, have a melting point of about 72° C.), and Bi₅₇Sn₄₃ (which may, for example, have a melting point of about 139° C.). As used herein, “Field's metal” refers to a eutectic, low-melting alloy of bismuth, indium, and tin. In certain exemplary embodiments, the Field's metal is In_(51.0)Bi_(32.5)Sn_(16.5). In other embodiments disclosed herein, the eutectic metal alloy may further include at least one organic vehicle, such as an organic solvent and/or a stabilizer as described herein.

The average particle size of the eutectic metal alloy nanoparticles may be about 1000 nanometers (nm) or less. In certain embodiments, the average particle size of the eutectic metal alloy nanoparticles may range from about 0.5 nm to about 1000 nm or from about 0.5 nm to less than about 1000 nm, such as from about 1 nm to about 750 nm, from about 10 nm to about 500 nm, from about 50 nm to about 400, from about 75 nm to about 250 nm, from about 100 nm to about 200 nm, or from about 100 nm to about 150 nm. In certain embodiments, the median diameter (D50) of the eutectic metal alloy nanoparticles may range from about 0.5 nm to about 1000 nm or from about 0.5 nm to less than about 1000 nm, such as from about 1 nm to about 750 nm, from about 10 nm to about 500 nm, from about 50 nm to about 400, from about 75 nm to about 250 nm, from about 100 nm to about 225 nm, or from about 150 nm to about 200 nm. The average particle size and median diameter of the particles may be determined by any suitable means, such as, for example, light microscopy, Scanning Electron Microscopy (SEM), or, for example, by using a Nanotrac® particle size analyzer.

The eutectic metal alloy nanoparticles disclosed herein may, in certain embodiments, have properties distinguishable from those of other conductive components often used in conductive composition, such as silver flakes. For example, the eutectic metal alloy nanoparticles disclosed herein may be characterized by a high surface tension. Further, the present eutectic metal alloy nanoparticles may have a lower melting point and a lower sintering temperature than silver flakes. The high surface tension prevents the eutectic metal alloy nanoparticles from flowing at temperatures above the melting temperature of the eutectic metal alloy. In order for the eutectic metal composition to flow, an external stimulus, such as pressure, may be placed on the composition. In embodiments, the conductive adhesive composition comprising eutectic metal alloy nanoparticles may be heated above the melting temperature of the eutectic metal alloy (i.e., ≥62° C.) and pressure may be applied to the composition in the form of placing a resistor chip onto the composition.

In embodiments disclosed herein, the surface tension of the conductive adhesive composition comprising eutectic metal alloy nanoparticles may range from about 20 nM/m to about 60 nM/m, such as about 25 nM/m to about 45 nM/m or about 30 nM/m to about 35 nM/m. Surface tension be measured in units of force per unit length (newtons per meter), energy per unit area (joules/square meter), or the contact angle between the solvent and a glass surface. Surface tension may be measured by any means known in the art, for example with a Kruss K-100 Tensiometer.

The eutectic metal alloy nanoparticle component of the conductive adhesive compositions disclosed herein may be present in any suitable or desired amount. In certain embodiments, the eutectic metal alloy nanoparticles, such as the Field's metal nanoparticles, are present in the conductive adhesive composition in an amount ranging from about 60% to about 95%, such as about 70% to about 90%, about 75% to about 85%, or about 80%, by weight based on the total solids weight of the conductive adhesive composition.

The eutectic metal alloy nanoparticles disclosed herein may be prepared by any suitable method. One exemplary method is to add pieces, such as centimeter sized chunks, of the eutectic metal alloy disclosed herein to a heated mixture comprising at least one solvent and at least one organic stabilizer, such as an organoamine stabilizer, until the alloy is molten and a mixture is formed. The mixture may then be dispersed by sonication and cooled. The eutectic metal alloy nanoparticles may then be isolated by decantation, rinsed, and dried.

Prior to, during, or after mixing the at least one organic stabilizer to the at least one solvent, the solvent may be heated, for example, to a temperature above the melting point of the eutectic metal alloy nanoparticles. In certain embodiments, the solvent may be heated to a temperature greater than about 55° C., such as about 60° C., about 65° C., about 70° C., or about 75° C.

The sonication can be performed by probe sonication or by bath sonication. Probe sonication refers to sonication wherein a probe is inserted into a container containing the mixture. Bath sonication refers to sonication wherein the container containing the mixture is placed into a bath, and the bath is subsequently sonicated. Probe sonication may provide greater energy and/or power compared to bath sonication.

In certain embodiments, the mixture may be sonicated at any suitable power, such as a power ranging from about 20% to about 100%, such as about 50% to about 90%, about 60% to about 80%, or, in certain embodiments, at about 100% power. The mixture may be sonicated for any suitable amount of time, such as, for example, from about 1 minute to about 1 hour, or, in certain embodiments, from about 2 minutes to about 45 minutes, about 5 minutes to about 20 minutes, or about 8 minutes to about 15 minutes. Any desired or effective sonicator can be used, such as a Branson Digital Probe Sonifier®. During sonication, the dispersion may be iced in order to cool the dispersion. In certain embodiments, the dispersion may be placed in an ice bath while sonicating in order to maintain the temperature of the dispersion below a certain temperature, such as, for example, below about 100° C., below about 85° C., or below about 75° C. After sonication, the dispersion may be cooled, for example cooled to about room temperature. The dispersed nanoparticles may then be collected, for example by centrifugation and decantation of the solvent, which may be repeated as necessary. Finally, the nanoparticles may be dried.

The at least one organic stabilizer that may be used in the preparation of the eutectic metal alloy nanoparticles disclosed herein may be physically or chemically associated with the surface of the eutectic metal alloy nanoparticles. In this way, the nanoparticles have the stabilizer thereon outside of a liquid solution. That is, the nanoparticles with the stabilizer thereon may be isolated and recovered from a reaction mixture solution used in forming the nanoparticles and stabilizer complex. The stabilized nanoparticles may thus be subsequently ready and homogenously dispersed in a solvent for forming a conductive adhesive composition as disclosed herein.

The organic stabilizer may interact with the eutectic metal alloy nanoparticle by a chemical bond and/or a physical attachment. The chemical bond may take the form of, for example, covalent bonding, hydrogen bonding, coordination complex bonding, ionic bonding, or a mixture of different chemical bonds. The physical attachment may take the form of, for example, van der Waals' forces, dipole-dipole interactions, or a mixture of different physical attachments.

The term “organic” in “organic stabilizer” refers to, for example, the presence of carbon, but, in addition to carbon, the organic stabilizer may include one or more non-metal heteroatoms such as nitrogen, oxygen, sulfur, silicon, halogen, and the like.

Exemplary organic stabilizers can include organoamines such as propylamine, butylamine, pentylamine, hexylamine, heptylamine, octylamine, nonylamine, decylamine, undecylamine, tridecylamine, tetradecylamine, pentadecylamine, hexadecylamine, heptadecylamine, octadecylamine, N,N-dimethylamine, N,N-dipropylamine, N,N-dibutylamine, N,N-dipentylamine, N,N-dihexylamine, N,N-diheptylamine, N,N-dioctylamine, N,N-dinonylamine, N,N-didecylamine, N,N-diundecylamine, N,N-didodecylamine, dodecylamine, methylpropylamine, ethylpropylamine, propylbutylamine, ethylbutylamine, ethylpentylamine, propylpentylamine, butylpentylamine, triethylamine, triethylenepentamine, tripropylamine, tributylamine, tripentylamine, trihexylamine, triheptylamine, trioctylamine, 1,2-ethylenediamine, N,N,N′,N′-tetramethylethylenediamine, propane-1,3-diamine, N,N,N′,N′-tetramethylpropane-1,3-diamine, butane-1,4-diamine, N,N,N′,N′-tetramethylbutane-1,4-diamine, diaminopentane, diaminoheptane, diaminooctane, diaminononane, diaminodecane, 2,2-(ethylenedioxy)diethylamine, 3-methoxypropylamine, pentaethylenehexamine, diethylenetriamine, tetraethylenepentamine, and the like or mixtures thereof. Exemplary organoamine stabilizers include butylamine, octylamine, dodecylamine 2,2-(ethylenedioxy)diethylamine, 3-methoxypropylamine, pentaethylenehexamine, tetraethylenepentamine, triethylenetetramine, and diethylenetriamine.

The extent of the coverage of the at least one organic stabilizer on the surface of the eutectic metal alloy nanoparticles may vary, for example, from partial to full coverage depending on the capability of the organic stabilizer to stabilize the nanoparticles.

The at least one solvent used in the preparation of the eutectic metal alloy nanoparticles may include, for example, propylene glycol methyl ether acetate, propylene glycol monomethyl ether acetate, toluene, di(propylene glycol) methyl ether acetate, (propylene glycol) methyl ether, di(propylene glycol) methyl ether, methyl isobutyl ketone, diisobutyl ketone, butyl acetate, methoxypropylacetate, propoxylated neopentylglycoldiacrylate, 1-phenoxy-2-propanol, and combinations thereof. In certain embodiments, the at least one polar solvent is propylene glycol methyl ether acetate. In embodiments, the solvent is not water, and in certain embodiments, the composition comprising a plurality of eutectic metal alloy nanoparticles is free of water. As used herein, “free of water,” indicates that the composition does not contain a detectable quantity of water or that the composition is anhydrous.

Surfactants

Any suitable or desired surfactant can optionally be included in the conductive adhesive compositions disclosed herein. In certain embodiments, the at least one surfactant is selected from the group consisting of silicone modified polyacrylates, polyester modified polydimethylsiloxanes, polyether modified polydimethylsiloxanes, polyacrylate modified polydimethylsiloxanes, polyester polyether modified polydimethylsiloxanes, low molecular weight ethoxylated polydimethylsiloxanes, polyether modified polydimethylsiloxanes, polyester modified polymethylalkylsiloxanes, polyether modified polymethylalkylsiloxanes, aralkyl modified polymethylalkylsiloxanes, polyether modified polymethylalkylsiloxanes, polyether modified polydimethylsiloxanes, and combinations thereof.

For example, the surfactant may be a polysiloxane copolymer that includes a polyester modified polydimethylsiloxane, commercially available from BYK-Chemie GmbH, Wesel, Germany with the trade name of BYK® 310; a polyether modified polydimethylsiloxane, commercially available from BYK-Chemie GmbH with the trade name of BYK® 330; a polyacrylate modified polydimethylsiloxane, commercially available from BYK Chemical with the trade name of BYK® Silclean® 3700 (about 25 weight percent in methoxypropylacetate); or a polyester polyether modified polydimethylsiloxane, commercially available from BYK-Chemie GmbH with the trade name of BYK® 375. The surfactant can also be a low molecular weight ethoxylated polydimethylsiloxane with the trade name Silsurf® A008 available from Siltech Corporation, Ontario, Canada. Some other examples of suitable surfactants may include BYK® 3500, BYK® 3510, BYK® 307, BYK® 333, BYK® Anti-Terra® U100, BYK® A-004, and BYK® C-409.

One or more surfactants can be provided in the conductive adhesive composition disclosed herein in any suitable or desired amount. In some embodiments, the surfactant is present in an amount ranging from about 0.01 to about 5 percent, such as from about 0.1 to about 3.5 percent, or from about 0.5 to about 2 percent, by weight, based on the total weight of the conductive adhesive composition.

Catalysts

The conductive adhesive compositions disclosed herein can optionally comprise at least one catalyst to enhance the curing process. Any suitable or desired catalyst can be selected for use in the present compositions. In certain embodiments, the at least one catalyst may be selected from the group consisting of amine salts of dodecylbenzene sulfonic acid (DDB SA), para toluene sulfonic acid, triflouromethane sulfonic acid, and combinations thereof.

The at least one catalyst can be provided in the conductive adhesive composition in any suitable or desired amount. In certain embodiments, the at least one catalyst is present in an amount ranging from about 0.05 to about 1.5 percent, such as from about 0.08 to about 1.0 percent, or from about 0.1 to about 0.5 percent, by weight, based on the total weight of the conductive adhesive composition.

Adhesion Promoters

In certain embodiments, the conductive adhesive composition disclosed herein may comprise at least one adhesion promoter, in any suitable or desired amount. Exemplary adhesion promoter that may be envisioned include Sartomer® CN132 (aliphatic diacrylate oligomer), and Sartomer® CN133 (aliphatic triacyl oligomer).

Solvents

Any suitable or desired solvent can be selected for the present conductive adhesive compositions. In some embodiments, the at least one solvent is selected from the group consisting of propylene glycol methyl ether acetate (PGMEA), di(propylene glycol) methyl ether acetate (Di-PGMEA), (propylene glycol)methyl ether (PGME), di(propylene glycol)methyl ether (Di-PGME), methyl isobutyl ketone (MIBK), diisobutyl ketone (DIBK), toluene, methyl isobutyl ketone, butylacetate, methoxypropylacetate, xylene, tripropyleneglycol monomethylether, dipropyleneglycol monomethylether, propoxylated neopentylglycoldiacrylate, and combinations thereof.

In certain embodiments, the solvent can be a non-polar organic solvent selected from the group consisting of hydrocarbons such as alkanes, alkenes, alcohols having from about 7 to about 18 carbon atoms such as undecane, dodecane, tridecane, tetradecane, hexadecane, 1-undecanol, 2-undecanol, 3-undecanol, 4-undecanol, 5-undecanol, 6-undecanol, 1-dodecanol, 2-dodecanol, 3-dedecanol, 4-dedecanol, 5-dodecanol, 6-dodecanol, 1-tridecanol, 2-tridecanol, 3-tridecanol, 4-tridecanol, 5-tridecanol, 6-tridecanol, 7-tridecanol, 1-tetradecanol, 2-tetradecanol, 3-tetradecanol, 4-tetradecanol, 5-tetradecanol, 6-tetradecanol, 7-tetradecanol, and the like; alcohols such as terpineol (α-terpineol), β-terpineol, geraniol, cineol, cedral, linalool, 4-terpineol, 3,7-dimethylocta-2,6-dien-1ol, 2-(2-propyl)-5-methyl-cyclohexane-1-ol; isoparaffinic hydrocarbons such as isodecane, isododecane; commercially available mixtures of isoparaffins such as Isopar® E, Isopar® G, Isopar® H, Isopar® L, Isopar® V, Isopar® G, manufactured by Exxon Chemical Company; Shellsol® manufactured by Shell Chemical Company; Soltrol® manufactured by Chevron Phillips Chemical Company; Begasol® manufactured by Mobil Petroleum Co., Inc.; IP Solvent 2835 manufactured by Idemitsu Petrochemical Co., Ltd; naphthenic oils; aromatic solvents such as benzene, nitrobenzene, toluene, ortho-, meta-, and para-xylene, and mixtures thereof; 1,3,5-trimethylbenzene (mesitylene); 1,2-, 1,3-, and 1,4-dichlorobenzene and mixtures thereof, trichlorobenzene; cyanobenzene; phenylcyclohexane and tetralin; aliphatic solvents such as isooctane, nonane, decane, dodecane; cyclic aliphatic solvents such as dicyclohexyl and decalin; and mixtures and combinations thereof.

In certain embodiments, two or more solvents can be used.

One or more solvents can be included in the conductive adhesive composition in any suitable or desired amount. In some embodiments, the solvent is present in an amount ranging from about 50 to about 90 percent, such as from about 60 to about 80 percent or from about 70 to about 80 percent, by weight, based on the total weight of the conductive adhesive composition.

Percent Solids

In some embodiments, the conductive adhesive compositions disclosed herein comprise from about 10 to about 60 weight percent solids, such as from about 15 to about 45 weight percent solids, or from about 20 to about 40 weight percent solids, based on the total weight of the composition in accordance with the present disclosure. In certain embodiments, the conductive adhesive composition contains a selected solids content of less than about 50 weight percent solids, based on the total weight of the instant composition. In certain embodiments, the eutectic metal alloy nanoparticles comprise about 60 weight percent to about 95 weight percent, such as from about 75 weight percent to about 90 weight percent, or about 80 weight percent to about 85 weight percent of the composition, based on the total solids weight of the composition.

Electronic Devices

In certain embodiments, disclosed herein is an electronic device including a substrate, a set of conductive terminals on the substrate, an electronic component opposite the substrate, a set of conductive terminals attached to the electronic component and facing the substrate, and a conductive adhesive composition, such as an anisotropic conductive adhesive composition, disposed between the electronic component and the substrate. The conductive adhesive composition may comprise conductive particles, such as eutectic metal alloy nanoparticles, distributed in an insulating medium in a substantially uniform manner.

An exemplary application of an anisotropic conductive adhesive composition includes a group of conductive elements. The composition is positioned between two sets of conductive terminals. A charge or field is generated by or passed through a substrate, which may be flexible, to the terminals. The field may pass from one terminal to another terminal through the anisotropic conductive adhesive composition. A top layer, such as an electronic component like a resistor, may comprise a set of conductive contact pads and may cover the anisotropic conductive adhesive composition and the terminals.

To create conductivity from the terminals to the electronic component through the conductive particles, the anisotropic conductive adhesive composition may be sandwiched between the top and bottom layers, i.e., between the substrate and the electronic component. When sandwiched in between, the conductive particles, such as eutectic metal alloy nanoparticles, may deform and provide a larger conductive surface area that contacts the terminals and conductive contact pad.

The substrate may be any suitable substrate including silicon, a glass plate, a plastic film, sheet, fabric, synthetic paper, or mixtures thereof. For structurally flexible devices, plastic substrates such as polyester, polycarbonate, polyimide sheets, polyethylene terephthalate (PET) sheets, polyethylene naphthalate (PEN) sheets, and the like, including mixtures thereof, may be used. The thickness of the substrate can be any suitable thickness, such as from about 10 micrometers to over 10 millimeters with an exemplary thickness being from about 50 micrometers to about 2 millimeters, especially for a flexible plastic substrate, and from about 0.4 to about 10 millimeters for a rigid substrate such as glass or silicon.

As shown in FIGS. 1 and 2, in certain exemplary embodiments of the electrical devices disclosed herein, there is a substrate 10, at least two areas formed from conductive ink 11 on the surface of the substrate 10, a conventional electronic component 15, such as a resistor, comprising at least two conductive contact pads 14 positioned over the at least two areas formed from conductive ink, and an adhesive conductive composition 12 disposed in between the conductive ink 11 and the conventional electronic component 15, wherein the adhesive conductive composition 12 comprises eutectic metal alloy nanoparticles 13.

In certain embodiments, the areas formed from conductive ink 11 may be spaced such that there is a gap 17 between a first area 11 and a second area 11 formed from conductive ink. In various embodiments of the disclosure, the adhesive conductive composition 12 comprising eutectic metal alloy nanoparticles 13 is not disposed inside the gap 17, such that the adhesive conductive composition 12 is on the surface of the areas formed from conductive ink 11. See, e.g., FIGS. 1A-C. In certain embodiments, the adhesive conductive composition 12 comprising eutectic metal alloy nanoparticles 13 is disposed inside the gap 17, such that the adhesive conductive composition 12 is both on the surface of the areas formed from conductive ink 11 and on the surface of the substrate 10. See, e.g., FIGS. 2A and 2B.

The conductive adhesive composition may be disposed on the substrate and/or conductive ink using any suitable method. For example, the present composition may be disposed on the substrate and/or conductive ink by solution depositing. Solution depositing as used herein refers to a process whereby a liquid is deposited upon the substrate to form a coating or layer. Solution depositing includes, for example, one or more of spin coating, dip coating, spray coating, slot die coating, flexographic printing, offset printing, screen printing, gravure printing or ink jet printing the conductive adhesive composition onto the substrate and/or conductive ink. In certain embodiments, the conductive adhesive composition is disposed on the substrate and/or conductive ink by ink jet printing.

In some embodiments, the conductive adhesive composition disposed on the substrate and/or the conductive ink is cured. The conductive adhesive composition can be cured at any suitable or desired temperature for any suitable period of time. In some embodiments, the conductive adhesive composition can be cured at a temperature ranging from about 80° C. to about 200° C., such as from about 100° C. to about 180° C., or from about 120° C. to about 160° C. for a period of time ranging from about 0.5 to about 6 hours, from about 1 to about 4 hours, or from about 2 to about 3 hours. In embodiments, the present composition can be cured at about 160° C. for about 6 hours or at about 200° C. for about 0.5 hours.

In some embodiments, the electronic device includes a conductive material. Any suitable or desired conductive material can be used to form conductive features on the present device. Typically, a conductive composition, such as a metal ink composition, is used to provide the conductive features, and suitable metal ink compositions may include, for example, silver nanoparticles dispersed within an ink vehicle, such as aromatic hydrocarbons including benzene, toluene, xylene and ethylbenzene. The fabrication of conductive features, such as an electrically conductive element, from a metal ink composition, for example, from a nanoparticle metal ink, such as a nanosilver ink composition, can be carried out by depositing the nanosilver ink composition, for example, onto a substrate using any suitable deposition technique including solution processing as described herein.

In some embodiments, the conductive features are formed by heating the conductive composition. In some embodiments, prior to heating, the layer of the deposited conductive composition may be electrically insulating or may have very low electrical conductivity; however, heating results in an electrically conductive layer composed of annealed metal particles, for example, such as annealed eutectic metal alloy nanoparticles, which increases the conductivity.

The deposited conductive composition, such as a metal ink composition, is heated to any suitable or desired temperature, such as from about 70° C. to about 250° C., or any temperature sufficient to induce annealing of the metal particles, for example, and thus form an electrically conductive layer, which is suitable for use as an electrically conductive element in electronic devices. The heating temperature is one that does not cause adverse changes in the properties of previously deposited layers or the substrate. In some embodiments, use of low heating temperatures allows use of low cost plastic substrates, which have an annealing temperature of below 140° C.

The heating can be for any suitable or desired time, such as from about 0.01 hours to about 10 hours. The heating can be performed in air, in an inert atmosphere, for example under nitrogen or argon, or in a reducing atmosphere, for example, under nitrogen containing from about 1 to about 20 percent by volume hydrogen. The heating can also be performed under normal atmospheric pressure or at a reduced pressure of, for example, about 1000 mbars to about 0.01 mbars.

Heating encompasses any technique that can impart sufficient energy to the heated material or substrate to anneal the metal nanoparticles, for example. These techniques include thermal heating (for example, at hot plate, an oven, and a burner), infra-red (“IR”) radiation, laser beam, flash light, microwave radiation, or ultraviolet (“UV”) radiation, or a combination thereof.

In some embodiments, after heating, an electrically conductive line, such as an electrically conductive silver line, is formed on the substrate that has a thickness ranging from about 0.1 to about 20 micrometers, or from about 0.15 to about 10 micrometers. In certain embodiments, after heating, the resulting electrically conductive line has a thickness of from about 0.1 to about 2 micrometers.

The conductivity of the conductive features, such as an electrically conductive line, that is produced by heating the deposited conductive composition is more than about 10,000 Siemens/centimeter (S/cm), more than about 50,000 S/cm, more than about 80,000 S/cm, more than about 100,000 S/cm, more than about 125,000 S/cm, more than about 150,000 S/cm or more than about 200,000 S/cm. Typically, the conductivity ranges from about 50,000 S/cm to about 200,000 S/cm, such as about 80,000 S/cm to about 150,000 S/cm, such as about 100,000 S/cm to about 125,000 S/cm.

The resistivity of the conductive features, such as an electrically conductive line, that is produced by heating the deposited conductive composition is less than about 1.0×10⁻⁴ ohms-centimeter (ohms-cm), less than about 2.0×10⁻⁵ ohms-cm, less than about 1.25×10⁻⁵ ohms-cm, less than about 1.0×10⁻⁵ ohms-cm, less than about 8.0×10⁻⁶ ohms-cm, less than about 6.6×10⁻⁶ ohms-cm or less than about 5.0×10⁻⁶ ohms-cm. Typically, the resistance ranges from about 2.0×10⁻⁵ ohms-cm to about 5.0×10⁻⁶ ohms-cm, such as about 1.25×10⁻⁵ ohms-cm to about 6.6×10⁻⁶ ohms-cm, such as about 1.0×10⁻⁵ ohms-cm to about 8.0×10⁻⁶ ohms-cm.

The device of the present disclosure may be used for any suitable or desired application, such as for electrodes, conductive pads, interconnects, conductive lines, conductive tracks, and the like, in electronic devices such as thin film transistors, organic light emitting diodes, printed antenna, and other electronic devices requiring conductive elements or components.

Cured Conductive Adhesive Compositions

Also provided herein is a cured conductive adhesive composition formed from a composition comprising at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, at least one melamine resin, eutectic metal alloy nanoparticles, and at least one solvent as described herein.

In some embodiments, the cured conductive adhesive comprises conductive features, such as an electrically conductive line, as described herein. In certain embodiments, the conductivity of the conductive features of the cured film is more than about 10,000 Siemens/centimeter (S/cm), more than about 50,000 S/cm, more than about 80,000 S/cm, more than about 100,000 S/cm, more than about 125,000 S/cm, more than about 150,000 S/cm or more than about 200,000 S/cm. For example, in certain embodiments, the conductivity of the cured conductive adhesive comprising the conductive features, such as an electrically conductive line, ranges from about 50,000 S/cm to about 200,000 S/cm, such as about 80,000 S/cm to about 150,000 S/cm, or about 100,000 S/cm to about 125,000 S/cm.

In some embodiments, the resistivity of the conductive features, such as an electrically conductive line of the cured conductive adhesive is less than about 1.0×10⁻⁴ ohms-centimeter (ohms-cm), less than about 2.0×10⁻⁵ ohms-cm, less than about 1.25×10⁻⁵ ohms-cm, less than about 1.0×10⁻⁵ ohms-cm, less than about 8.0×10⁻⁶ ohms-cm, less than about 6.6×10⁻⁶ ohms-cm, or less than about 5.0×10⁻⁶ ohms-cm. In certain embodiments, the resistivity of the cured conductive adhesive comprising the conductive features, such as an electrically conductive line, ranges from about 2.0×10⁻⁵ ohms-cm to about 5.0×10⁻⁶ ohms-cm, such as about 1.25×10⁻⁵ ohms-cm to about 6.6×10⁻⁶ ohms-cm, or about 1.0×10⁻⁵ ohms-cm to about 8.0×10⁻⁶ ohms-cm.

Methods of Forming Conductive Elements

The conductive adhesive compositions disclosed herein may be prepared by mixing the eutectic metal alloy nanoparticle component with a first component comprising the at least one epoxy resin, at least one polymer chosen from polyvinyl phenols and polyvinyl butyrals, the at least one melamine resin, and the at least one solvent, as disclosed herein.

Also provided herein is a process for forming conductive features, such as an electrically conductive line as described herein, on a substrate including depositing a conductive adhesive composition onto a substrate and/or conductive element, such as a conductive ink, as described herein, and curing the conductive adhesive composition to form a cured conductive adhesive. The conductive features can be fabricated by any suitable or desired method. In certain embodiments, the conductive features can be prepared by solution processing techniques such as ink jet printing on the substrates with a pre-applied interlayer. The conductive features show high conductivity with significantly improved adhesion after annealing at a suitable temperature.

In certain embodiments, the conductive adhesive composition is deposited onto a substrate and/or conductive element by ink jet printing. For example, in certain embodiments, aerosol jet printing is used for deposition. As used herein, “aerosol jet printing” refers to a process that involves atomization of the conductive adhesive composition, producing droplets on the order of one to two microns in diameter. The atomized droplets may be entrained in a gas stream and delivered to a print head. At the print head, an annular flow of gas may be introduced around the aerosol stream to focus the droplets into a tightly collimated beam. The combined gas streams may then exit the print head through a converging nozzle that compresses the aerosol stream to a small diameter, for example a diameter ranging from about 1 micron to about 10 microns. The jet exits the print head and is deposited on a substrate or other surface. The resulting patterns can have features ranging from about 5 microns to about 3000 microns wide, with layer thickness ranging from tens of nanometers to about 25 microns, such as from about 1 micron to about 20 microns.

Notwithstanding that the numerical ranges and parameters setting forth the broad scope of the disclosure are approximations, the numerical values set forth in the specific examples are reported as precisely as possible. Any numerical value, however, inherently contains certain errors necessarily resulting from the standard deviation found in their respective testing measurements. Moreover, all ranges disclosed herein are to be understood to encompass any and all sub-ranges subsumed therein.

While the present teachings have been illustrated with respect to one or more implementations, alterations and/or modifications can be made to the illustrated examples without departing from the spirit and scope of the appended claims. In addition, while a particular feature of the present teachings may have been disclosed with respect to only one of several implementations, such feature may be combined with one or more other features of the other implementations as may be desired and advantageous for any given or particular function. Furthermore, to the extent that the terms “including,” “includes,” “having,” “has,” “with,” or variants thereof are used in either the detailed description and the claims, such terms are intended to be inclusive in a manner similar to the term “comprising.” Further, in the discussion and claims herein, the term “about” indicates that the value listed may be somewhat altered, as long as the alteration does not result in nonconformance of the process or structure to the illustrated embodiment. Finally, “exemplary” indicates the description is used as an example, rather than implying that it is an ideal.

It will be appreciated that variants of the above-disclosed and other features and functions, or alternatives thereof, may be combined into many other different systems or applications. Various presently unforeseen or unanticipated alternatives, modifications, variations, or improvements therein may be subsequently made by those skilled in the art which are also intended to be encompasses by the following claims.

EXAMPLES

The following Examples are being submitted to further define various species of the present disclosure. These Examples are intended to be illustrative only and are not intended to limit the scope of the present disclosure. Parts and percentages are by weight unless otherwise indicated.

Example 1A—Preparation of Base Adhesive Composition

Base adhesive solutions were prepared containing the formulation as set forth in Table 1 below.

TABLE 1 Formulation of Base Solution PLGDE Di-PGMEA (Mn 380) PMMF PVP PGMEA solvent Di-PGME Solid Total (g) (g) (g) (g) (g) (g) (%) (wt %) 13.2 2.8 2.5 16.5 15.0 37.0 50.0 35.7 7.6 6.7 50.0 50.0 100.0 13.2 3.75 3.75 29.30 50.0 PLGDE—polypropylene glycol diglycidyl ether PMMF—poly(melamine-co-formaldehyde) PVP—polyvinyl phenol PGMEA—propylene glycol methyl ether acetate Di-PGMEA—di(propylene glycol) methyl ether acetate Di-PGME—di(propylene glycol)methyl ether

A 60 mL bottle (Bottle A) and a 125 mL bottle (Bottle B) were air-blown to clean, and a magnetic stir bar was added into each bottle. Bottle B and its lid were weighed, and the weight recorded. 16.5 g of di(propylene glycol) methyl ether acetate (Di-PGMEA) solvent was loaded into Bottle A, and then 2.8 g poly(melamine-co-formaldehyde) (PMMF) was added. Bottle A was stirred at 250 rpm and run for at least 5 minutes until the PMMF was completely dissolved. Next, 15 g of di(propylene glycol)methyl ether (Di-PGME) solvent was added to Bottle B, followed by 13.2 g polypropylene glycol diglycidyl ether (PLGDE), and the solution was mixed for at least 5 minutes.

The contents of Bottle A and Bottle B were combined by pouring the solution of Bottle A into Bottle B, and the combined solutions were mixed for about 30 minutes. Next, 2.5 g of polyvinyl phenol (PVP) was slowly added into Bottle B and then mixed for two hours, until all of the PVP powder was dissolved.

Example 1B—Preparation of Conductive Adhesive Composition

To a 30 mL bottle was loaded 7.5 g of a base adhesive composition, having a solids content of 2.775 g (7.5 g×37%) and 7.5 g of di(ethylene glycol) methyl ether (Di-PGME) and di(ethylene glycol methyl ether acetate (Di-PGMEA) mixture at a ratio of 1:1. The bottle was then put on a Vortex for 5 seconds at a setting speed of 3000 rpm. Next, the bottle was rolled on a Roller for about 5 minutes. 10 g of Field's Metal particles were added, such that the amount of Field's Metal after drying was about 78.3% (10/(10+7.5*0.37)*100). The bottle was put on a Vortex for 10 seconds at a setting speed of 3000 rpm, and then stirred with a magnetic rod overnight. The resultant sample was placed into a water bath sonicator for 10 minutes before aerosol print testing.

Example 1C—Characterization of Conductive Adhesive Composition

The conductive adhesive composition prepared in Example 1B was evaluated to analyze the Field's Metal particle size distribution, as well as other physical characteristics of the composition. Field's Metal nanoparticles were synthesized using tetraethylenepentamine as the organoamine stabilizer. Particle size was analyzed using a Nanotrac® U2275E, and the results are shown below in Tables 2A and 2B. The median diameter (D50) was 193 nm (0.193 μm), and 98.1% of the particles were <192 nm (0.1918 μm) with an average particle size of 148.6 nm (0.1486 μm).

TABLE 2A Particle Size Distribution for Eutectic Metal Alloy Nanoparticles with Tetraethylenepentamine Percentile Size (nm) 10% 129.2 20% 151.2 30% 166.3 40% 179.7 50% 193.1 60% 208.8 70% 230.0 80% 259.4 90% 304.0 95% 343.0

TABLE 2B Particle Size Distribution for Eutectic Metal Alloy Nanoparticles with Tetraethylenepentamine Size (nm) % Channel % Pass 6,540 0.0 100 5,500 0.0 100 4,620 0.0 100 3,890 0.0 100 3,270 0.0 100 2,750 0.0 100 2,312 0.0 100 1,944 0.0 100 1,635 0.84 100 1,375 0.0 99.16 1,156 0.04 99.16 972 0.56 99.12 818 0.47 98.56 687 0.0 98.09 578 0.0 98.09 486 0.22 98.09 409 2.80 97.87 344 7.90 95.07 289 12.28 87.17 243 17.35 74.89 204.4 23.47 57.54 171.9 17.83 34.07 144.5 8.55 16.24 121.5 4.36 7.69 102.2 2.72 3.33 85.9 0.61 0.61 72.3 0.0 0.0 60.8 0.0 0.0 51.1 0.0 0.0 43.0 0.0 0.0 36.1 0.0 0.0

Rheology.

The rheology of the conductive adhesive composition prepared in Example 1B was measured. The composition had an average shear viscosity (40-400 s⁻¹) of 7.0 cps. The viscosity measurements are shown below in Table 3. An ARES-G2 Rheometer was used to measure the viscosity.

TABLE 3 Viscosity of Conductive Adhesive Composition Shear Rate Range (s⁻¹) 4-400 10-400 40-400 1-6.3 Shear Index 0.94 0.96 0.99 0.97 Mean Viscosity 6.85 6.92 7.00 6.42 s viscosity 0.20 0.15 0.08 0.06 CV viscosity 2.9 2.2 1.1 0.9

Surface Tension.

Surface tension was measured to be 32 mN/m using a K100 Force Tensiometer by Krüss.

Printing of Conductive Adhesive Composition.

The conductive adhesive composition was jetted using an Optomec Aerosol Jet System in Pneumatic Aerosol mode (PA). A 300 μm nozzle was used with a 3 mm offset distance between the nozzle and the substrate. The printing rate was maintained at 10 mm/s. The following gas flow parameters were used to print the conductive adhesive composition: Sheath Gas=40 cm³/min, Atomization Gas=650 cm³/min, Exhaust gas=650 cm³/min. The conductive adhesive composition was jetted onto flexible polycarbonate and rigid polycarbonate substrates.

Resistance Test Measurements.

A test pattern was printed with silver nanoparticle ink on polycarbonate. There were two lines each terminated in a pad. Between the two pads was a 5 mm gap. The conductive adhesive composition was tested in two ways. In the first test, the conductive adhesive composition was printed only on the pads (and not in the gap) (see FIG. 1A), the substrate was heated to about 65° C., and a resistor was placed across the gap of the silver printed pads (see FIG. 1B), applying pressure to the resistor to make the Field's metal particles flow (see FIG. 1C). The conductive adhesive composition was cured at 120° C. for 2 hours.

In the second test, the conductive adhesive composition was printed on the pads and across the gap (see FIG. 2A), the substrate was heated to about 65° C., and a resistor was placed across the gap of the silver printed pads, applying pressure to the resistor to make the Field's metal particles flow (see FIG. 2B). The conductive adhesive composition was cured at 120° C. for 2 hours.

For both tests, the gap was spanned by a surface mount 100Ω resistor. The conductive adhesive was evaluated by measuring the resistance across the two silver lines. The leads of the digital multimeter were placed on either side of the gap on the conductive silver lines. The adhesive is deemed sufficiently conductive if the measured resistance is 100Ω, indicating that the conductive adhesive is not contributing additional resistance. When the conductive adhesive was printed on the silver pads and across the gap between the pads, the multimeter measured 101.3Ω, indicating that the conductive adhesive does not significantly contribute additional resistance to the “circuitry” (1%). When the conductive adhesive was printed on the silver pads only and 1Ω resistors were used to bridge the gap between the pads, the multimeter measured about 1.5Ω, indicating that the conductive adhesive does not significantly contribute additional resistance to the “circuitry.” While not wishing to be bound by theory, it is hypothesized that the extra 1.3Ω or 0.5Ω could be from resistance in the silver lines, the contact resistance between the probes and the silver lines, from the conductive adhesive, or a combination of these possibilities. Given that a resistance was measured indicates that the adhesive was functioning anisotropically, since there is no shorting across the gap (i.e., there is not a conductive pathway in the region between the gap even though there was adhesive.

Adhesion Test.

Adhesion was assessed qualitatively using several steps in attempts to remove the resistor from the silver pads, in increasing amounts of applied force. First, the polycarbonate plaque was turned over. Second, the back of the plaque was tapped with the three fingers. Third, the plaque was turned on its side and the tapped on a table. Finally, force was applied to the resister using tweezers to pop it off. The cured conductive adhesive composition required applied force (i.e., the use of tweezers) to remove the resistor from the silver pads. The resistor was not removed by merely turning the plaque over, tapping the back of the plaque with fingers, or tapping the plaque on a table. This demonstrates that the cured conductive adhesive composition had adequate adhesion. 

What is claimed is:
 1. A conductive adhesive composition comprising: at least one epoxy resin; at least one polymer chosen from the group consisting of polyvinyl phenols and polyvinyl butyrals; at least one melamine resin; a plurality of eutectic metal alloy nanoparticles having an average particle size of about 1000 nanometers or less; and at least one solvent present in an amount ranging from about 60% to about 90% based on a total weight of the conductive adhesive composition, wherein the conductive adhesive composition does not comprise any additional conductive element other than the plurality of eutectic metal alloy nanoparticles, wherein the plurality of eutectic metal alloy nanoparticles is present in the conductive adhesive composition in an amount ranging from about 60% to about 95%, based on a total solids weight of the conductive adhesive composition, and wherein the at least one solvent is selected from the group consisting of propylene glycol methyl ether acetate, di(propylene glycol) methyl ether acetate, (propylene glycol)methyl ether, di(propylene glycol)methyl ether, methyl isobutyl ketone, diisobutyl ketone, and 1-phenoxy-2-propanol.
 2. The conductive adhesive composition of claim 1, wherein the plurality of eutectic metal alloy nanoparticles comprise Field's metal.
 3. The conductive adhesive composition of claim 1, wherein the plurality of eutectic metal alloy nanoparticles further comprise at least one organoamine stabilizer selected from the group consisting of butylamine, octylamine, 3-methoxypropylamine, pentaethylenehexamine, 2,2-(ethylenedioxy)diethylamine, tetraethylenepentamine, triethylenetetramine, and diethylenetriamine.
 4. The conductive adhesive composition of claim 1, having a solids content ranging from about 20% to about 80%, based on a total weight of the conductive adhesive composition.
 5. The conductive adhesive composition of claim 1, wherein the at least one melamine resin is selected from the group consisting of a methylated poly (melamine-co-formaldehyde), butylated poly(melamine-co-formaldehyde), isobutylated poly (melamine-co-formaldehyde), acrylated poly(melamine-co-formaldehyde), and methylated and butylated poly(melamine-co-formaldehyde).
 6. The conductive adhesive composition of claim 1, wherein the composition has a viscosity ranging from about 2 cps to less than about 300 cps at a temperature of about 20° C. to about 30° C.
 7. The conductive adhesive composition of claim 1, wherein the at least one epoxy resin is selected from the group consisting of bisphenol A diglycidyl ether, bisphenol A propoxylate diglycidyl ether, glycidyl epoxy resins, trimethylolpropane triglycidyl ether, neopentyl glycol diglycidyl ether, poly(propylene glycol) diglycidyl ether, tris-(hydroxyl phenyl) -methane-based epoxy resins, and cycloaliphatic epoxides.
 8. The conductive adhesive composition of claim 1, further comprising at least one adhesion promoter.
 9. The conductive adhesive composition of claim 1, wherein the at least one polymer is a polyvinyl phenol selected from the group consisting of poly(4-vinylphenol), poly-p-vinylphenol, poly(vinylphenol)/poly(methyl acrylate), poly(vinylphenol)/poly(methyl methacrylate), and poly(4-vinylphenol)/poly(vinyl methyl ketone).
 10. The conductive adhesive composition of claim 1, wherein the conductive adhesive composition is jettable by inkjet or aerosol jet printing.
 11. An electronic device comprising: a substrate; conductive features disposed on the substrate; a conductive electrical component disposed over the conductive features; and the conductive adhesive composition according to claim 1 disposed between the conductive features and the conductive electrical component.
 12. The electronic device of claim 11, wherein the substrate is selected from the group consisting of silicon, glass, plastics, sheets, fabrics, synthetic papers, and mixtures thereof.
 13. The electronic device of claim 11, wherein the substrate is selected from the group consisting of polyester, polycarbonate, polyimide sheets, polyethylene terephthalate sheets, polyethylene naphthalate sheets, and mixtures thereof.
 14. The electronic device of claim 11, wherein the conductive features comprise an electrically conductive element formed from a metal nanoparticle conductive ink composition.
 15. The electronic device of claim 14, wherein the metal nanoparticle conductive ink composition is a silver nanoparticle conductive ink composition.
 16. The electronic device of claim 11, wherein the conductive adhesive composition has a viscosity ranging from about 2 cps to about 300 cps at a temperature of about 20° C. to about 30° C.
 17. A method of making a conductive adhesive composition comprising according to claim 1: mixing at least one epoxy resin, at least one polymer chosen from the group consisting of polyvinyl phenols and polyvinyl butyrals; at least one melamine resin; and at least one solvent present in an amount ranging from about 60% to about 90% based on a total weight of the conductive adhesive composition, to create a mixture; and adding a plurality of eutectic metal alloy nanoparticles having an average particle size of about 1000 nanometers or less to the mixture to create a conductive adhesive composition, wherein the conductive adhesive composition does not comprise any additional conductive element other than the plurality of eutectic metal alloy nanoparticles, wherein the plurality of eutectic metal alloy nanoparticles is present in the conductive adhesive composition in an amount ranging from about 60% to about 95%, based on a total solids weight of the conductive adhesive composition, and wherein at least one solvent is selected from the group consisting of propylene glycol methyl ether acetate, di(propylene glycol) methyl ether acetate, (propylene glycol)methyl ether, di(propylene glycol)methyl ether, methyl isobutyl ketone, diisobutyl ketone, and 1-phenoxy-2-propanol.
 18. The method of claim 17, wherein the plurality of eutectic metal alloy nanoparticles comprise a Field's metal alloy.
 19. The method of claim 17, wherein the conductive adhesive composition has a solids content ranging from about 20% to about 80%, based on a total weight of the conductive adhesive composition. 